EP4033006A1 - Tôle d'acier électromagnétique non orientée - Google Patents

Tôle d'acier électromagnétique non orientée Download PDF

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Publication number
EP4033006A1
EP4033006A1 EP20865827.8A EP20865827A EP4033006A1 EP 4033006 A1 EP4033006 A1 EP 4033006A1 EP 20865827 A EP20865827 A EP 20865827A EP 4033006 A1 EP4033006 A1 EP 4033006A1
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EP
European Patent Office
Prior art keywords
steel sheet
insulating coating
coating film
phosphate
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20865827.8A
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German (de)
English (en)
Other versions
EP4033006A4 (fr
Inventor
Kazutoshi Takeda
Shuichi Yamazaki
Takuya Matsumoto
Hiroyasu Fujii
Masaru Takahashi
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Nippon Steel Corp
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Nippon Steel Corp
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Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Publication of EP4033006A1 publication Critical patent/EP4033006A1/fr
Publication of EP4033006A4 publication Critical patent/EP4033006A4/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1233—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants

Definitions

  • the present invention relates to a non-oriented electrical steel sheet.
  • Non-oriented electrical steel sheets are typically provided with insulating coating films.
  • various coating properties are required for insulating coating films such as corrosion resistance, adhesiveness, heat resistance for resisting annealing, and stability as coatings.
  • insulating coating films are blended with a chromate, and thereby the coating properties are provided at an extremely high level.
  • amid growing awareness of environmental issues insulating coating films without chromates have recently been developed.
  • Patent Documents 1 and 2 disclose a non-oriented electrical steel sheet including an insulating coating film that mainly contains an organic resin and a metal phosphate of one type selected from specific metal elements.
  • Patent Document 3 discloses a surface treatment agent for a non-oriented electrical steel sheet, the surface treatment agent containing phosphorus acid aluminum, organic resin, and OH-containing organic compound that are blended together in a specific ratio.
  • Patent Document 4 discloses a method for producing an electrical steel sheet with an insulating coating film, the method including performing phosphoric acid pickling treatment and drying treatment and then forming a phosphate compound coating on a surface of a steel sheet, in which the drying treatment is performed based on a predetermined relation between temperature and drying time.
  • the insulating coating film has improved punchability (i.e., workability) while exerting an excellent insulation property but is still susceptible to improvement for providing an insulating coating film that further combines adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance.
  • Patent Document 4 provides excellent appearance and adhesiveness but involves a problem of industrial productivity because the technique requires pickling treatment with phosphorus acid to be performed in advance and requires the drying treatment to be performed after the pickling treatment.
  • An objective of the present invention which has been made in view of such a problem, is to provide a non-oriented electrical steel sheet including an insulating coating film that is excellent in insulation property, workability, adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance without containing a chromate.
  • the present invention has been made to solve the above problem, and the gist thereof is a non-oriented electrical steel sheet to be described below.
  • non-oriented electrical steel sheet including an insulating coating film that is excellent in insulation property, workability, adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance without containing a chromate.
  • the present inventors conducted intensive studies about a method for providing an insulating coating film that combines insulation property, workability, adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance and consequently came to obtain the following findings.
  • FIG 1 is a schematic diagram for describing a structure of a non-oriented electrical steel sheet according to the present embodiment.
  • a non-oriented electrical steel sheet 1 includes a base metal steel sheet 11 and insulating coating films 13 that are formed on surfaces of the base metal steel sheet 11. Although the insulating coating films 13 are provided on the surfaces on both sides of the base metal steel sheet 11 in a thickness direction of the base metal steel sheet 11 in Figure 1 , an insulating coating film 13 may be provided on only a surface of one side of the base metal steel sheet 11.
  • non-oriented electrical steel sheet 11 there is no particular limitation on a steel type of the base metal steel sheet 11 used for the non-oriented electrical steel sheet 1.
  • Si silicon is an element that increases electric resistance and improves magnetic properties when its content is 0.1 mass% or more. As the content of Si increases, the magnetic properties are improved, but at the same time, brittleness tends to increase with an increase in the electric resistance. The increase in brittleness becomes prominent when the content of Si becomes more than 4.0 mass%, and the content of Si is thus preferably 4.0 mass% or less.
  • Al is an element that increases electric resistance and improves magnetic properties when its content is 0.05 mass% or more. As the content of Al increases, the magnetic properties are improved, but at the same time, rolling properties tend to decrease with an increase in the electric resistance. The decrease in rolling properties becomes prominent when the content of Al becomes more than 3.0 mass%, and the content of Al is thus preferably 3.0 mass% or less.
  • non-oriented electrical steel sheet has the content of Si and the content of Al described above, there is no particular limitation on the non-oriented electrical steel sheet, and various types of known non-oriented electrical steel sheets can be used as the base metal steel sheet 11.
  • Mn manganese
  • contents of other elements such as S (sulfur), N, (nitrogen), and C (carbon) are preferably less than 100 ppm in total, more preferably less than 30 ppm.
  • an ingot (e.g., slab) having the chemical composition is subjected to hot rolling and coiled into a coil as a hot-rolled sheet, annealed within the temperature range of 800 to 1050°C as being in a state of the hot-rolled sheet when necessary, then subjected to cold rolling to have a thickness of 0.15 to 0.50 mm, and further annealed to be produced into a base metal steel sheet, which is preferably used as the base metal steel sheet 11.
  • a sheet thickness of the base metal steel sheet 11 is more preferably 0.25 mm or less.
  • its annealing temperature is preferably within the range of 750 to 1000°C.
  • the base metal steel sheet 11 preferably has a relatively small surface roughness because a small surface roughness gives favorable magnetic properties.
  • arithmetic average roughnesses (Ra) in a rolling direction and a direction perpendicular to the rolling direction are both preferably 1.0 ⁇ m or less, more preferably 0.1 to 0.5 ⁇ m. This is because Ra being more than 1.0 ⁇ m tends to cause deterioration in the magnetic properties.
  • the insulating coating film 13 is formed at least on the surface on one side of the base metal steel sheet 11.
  • the insulating coating film is an insulating coating film that mainly contains a metal phosphate, an organic resin, and a water-soluble organic compound to be described below in detail and does not contain chromium.
  • the insulating coating film contains the metal phosphate, the organic resin, and the water-soluble organic compound at 50 mass% or more in total with respect to the total mass of the insulating coating film. Each component will be described below in detail.
  • the metal phosphate contained in the insulating coating film becomes solid content when a solution (e.g., aqueous solution, etc.) mainly containing a phosphoric acid and metal ions is dried and functions as a binder in the insulating coating film.
  • a solution e.g., aqueous solution, etc.
  • various types of known phosphoric acids can be used; for example, orthophosphoric acid, metaphosphatic acid, polyphosphoric acid, or the like is preferably used.
  • the solution of the metal phosphate can be prepared by mixing at least any one of oxides, carbonates, and hydroxides of metal ions into one of the various types of the phosphoric acids.
  • the metal phosphate contains Al (aluminum) as a metallic element.
  • the insulating coating film contains a metal phosphate of Al (i.e., aluminum phosphate).
  • the content of the aluminum phosphate is preferably 10 parts by weight or more per 100 parts by weight of the metal phosphate.
  • a degree of crystallinity of the aluminum phosphate calculated from peaks from the metal phosphate is within a range of 0.5 to 5.0%.
  • the degree of crystallinity is an index that takes 100% when the aluminum phosphate is all crystallized and takes 0% when the aluminum phosphate is all amorphous.
  • the degree of crystallinity of the aluminum phosphate in the insulating coating film according to the present embodiment being within the range of 0.5 to 5.0% means that the aluminum phosphate is little crystallized and is present in a state that the aluminum phosphate is almost amorphous.
  • the degree of crystallinity of the aluminum phosphate is more than 5.0%, unevenness of a crystal face of the crystallized aluminum phosphate becomes prominent, resulting in a decrease in space factor or a decrease in adhesiveness and/or workability.
  • the degree of crystallinity of the aluminum phosphate is as excessively low as less than 0.5%, there is a surplus of bonds of the metal phosphate, which will bind to water to accelerate moisture absorption, resulting in a deterioration in hygroscopic resistance.
  • the degree of crystallinity of the aluminum phosphate By controlling the degree of crystallinity of the aluminum phosphate to be within the range of 0.5 to 5.0%, crystals of the aluminum phosphate are rendered in a polycrystal in a fine state, making it possible to provide a close-grained insulating coating film.
  • the degree of crystallinity of the aluminum phosphate is preferably 4.0% or less, more preferably less than 2.0%, still more preferably 1.0% or less.
  • the degree of crystallinity of the aluminum phosphate can be controlled to be within a desired range by introducing a factor that restrains growth of grains, into the insulating coating film.
  • the insulating coating film contains types of metal phosphate that are similar to one another, crystallization of the metal phosphate is often restrained.
  • the metal phosphate preferably further contains, in addition to Al, a divalent metallic element M other than aluminum.
  • a divalent metallic element M can be one or more types selected from the group consisting of, for example, Zn, Co, Mg, Mn, and Ni.
  • the metal phosphate more preferably contains aluminum and zinc as metallic elements (in other words, more preferably contains aluminum phosphate and zinc phosphate).
  • Figure 2 illustrates an example of an XRD spectrum of the non-oriented electrical steel sheet according to the present embodiment
  • Figure 3 is a schematic diagram for describing a degree of crystallinity of an insulating coating film.
  • Figure 2 illustrates an XRD spectrum of a non-oriented electrical steel sheet that includes aluminum phosphate, an example of the metal phosphate, in a form of an insulating coating film.
  • An XRD peak of a metal phosphate differs depending on a metallic element included in the metal phosphate.
  • An XRD peak of the metal phosphate in question in the present embodiment is observed at a vicinity of the following angle, for example.
  • the peaks from the aluminum phosphate are as schematically illustrated in Figure 3 .
  • the peaks of the aluminum phosphate include a background attributable to diffraction by the air and the like (a part corresponding to an integrated intensity A 0 in Figure 3 ), a broad peak attributable to the metal phosphate in an amorphous state (a part corresponding to an integrated intensity A a in Figure 3 ), and peaks attributable to the aluminum phosphate in a crystalline state (parts corresponding to integrated intensities A c1 + A c2 in Figure 3 ).
  • the XRD spectrum of the non-oriented electrical steel sheet can be obtained by performing measurement with a commercially available X-ray diffractometer, and there is no particular limitation on conditions for the measurement; however, for example, the XRD spectrum of the non-oriented electrical steel sheet can be obtained by performing the measurement under the following measurement conditions. That is, the measurement is performed with the apparatus SmartLab from Rigaku Corporation, under conditions of using Cu tube, a voltage of 40 kV, a current of 30 mA, a measurement angle (2 ⁇ ) 5 to 90°, a step of 0.02°, a scanning mode of 4°/min, and an entrance slit of 1/2 deg.
  • the organic resin contained in the insulating coating film is present in a state of being dispersed in the metal phosphate functioning as a binder.
  • the presence of the organic resin in the metal phosphate makes it possible to restrain grains of the metal phosphate from growing to be large and accelerate the polycrystallization of the metal phosphate, enabling the formation of a close-grained insulating coating film.
  • the organic resin is to have an SP value that is within a range of 18.0 (MPa) 0.5 or more to less than 24.0 (MPa) 0.5 .
  • the SP value of the organic resin is excessively low, the organic resin becomes likely to be separated from the metal phosphate in general; as a result, the metal phosphate becomes likely to be crystallized, and the degree of crystallinity of the aluminum phosphate tends to increase.
  • the organic resin becomes likely to be mixed with the metal phosphate, which significantly hampers the metal phosphate from being crystallized, and the degree of crystallinity of the aluminum phosphate tends to decrease to excess.
  • the SP value of the organic resin is more preferably within a range of 19.0 (MPa) 0.5 or more to less than 23.5 (MPa) 0.5 , still more preferably within a range of 20.0 (MPa) 0.5 or more to less than 23.0 (MPa) 0.5 .
  • the SP value is what is called a solubility parameter.
  • the solubility parameter adopted in the present invention is a thermodynamic physical quantity that represents a scale for compatibility between substances, and it is known that substances having similar SP values tend to dissolve in each other.
  • the solubility parameter adopted in the present invention is called Hildebrand solubility parameter, which is generally measured by the cloud method.
  • an organic resin is dissolved in advance in one solvent with a known SP value that causes the organic resin to be dissolved well therein, then, another solvent with an SP value that is known but different from that of the one solvent is gradually dropped, and an SP value of the organic resin is calculated from the SP values of the solvents and amounts of the solvents required to cause the organic resin to precipitate to cloud the solution.
  • organic resin there is no particular limitation on the type of the organic resin as long as its SP value is within the range described above, and one, or two or more types of various known organic resins such as acrylic resin, polystyrene resin, vinyl acetate resin, epoxy resin, polyurethane resin, polyamide resin, phenolic resin, melamine resin, silicon resin, polypropylene resin and polyethylene resin, can be used.
  • various known organic resins such as acrylic resin, polystyrene resin, vinyl acetate resin, epoxy resin, polyurethane resin, polyamide resin, phenolic resin, melamine resin, silicon resin, polypropylene resin and polyethylene resin, can be used.
  • acrylic resin is obtained by copolymerizing (more specifically, emulsion polymerization of) monomer or oligomer of the acrylic resin in the present of nonionic surfactant in which molecules each have a radically polymerizable unsaturated group (which can be regarded as reactive surfactant).
  • a dispersion liquid (emulsion) obtained by dispersing the resulting acrylic copolymer in a dispersion medium such as water is used.
  • nonionic surfactant for example, one of surfactants having a radically polymerizable unsaturated group such as (meth)allyl group, (meth) acrylic group, a styryl group and having the number of moles added of an alkylene oxide being within a range of 20 to 55 can be used, or two or more of the surfactants can be used in combination.
  • an acrylic resin as the organic resin, it is possible to accelerate polycrystallization of the metal phosphate more reliably, making it possible to provide a more close-grained insulating coating film.
  • Examples of available monomers for the copolymerization of the acrylic resin used in the present embodiment include, but not particularly limited to, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, n-decyl acrylate, and n-dodecyl acrylate.
  • acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, and the like can be used as monomers with a functional group
  • 2-hydroxylethyl(meth)acrylate, 2-hydroxylpropyl(meth)acrylate, 3-hydroxylbutyl(meth)acrylate, 2-hydroxylethyl(meth)allylether, and the like can be used as monomers with a hydroxyl group.
  • the acrylic resin according to the present embodiment can be formulated such that its SP value falls within a prescribed range by performing an emulsion polymerization process using the nonionic surfactant or combining various monomers.
  • the water-soluble organic compound contained in the insulating coating film is an organic compound that is water-soluble and compatible with an inorganic solution of a metal phosphate or the like, such as alcohol, ester, ketone, ether, carboxylic acid, and sugar.
  • a metal phosphate or the like such as alcohol, ester, ketone, ether, carboxylic acid, and sugar.
  • the water-soluble organic compound used in the present embodiment is a water-soluble organic compound having an SP value that is within a range of 19.0 (MPa) 0.5 or more to less than 35.0 (MPa) 0.5 .
  • SP value a stability of a metal ion in the metal phosphate increases in general; as a result, the metal phosphate becomes likely to be crystallized, and the degree of crystallinity of the aluminum phosphate tends to increase.
  • the SP value of the water-soluble organic compound is more preferably within a range of 20.0 (MPa) 0.5 or more to less than 34.5 (MPa) 0.5 , still more preferably within a range of 24.0 (MPa) 0.5 or more to less than 34.0 (MPa) 0.5 .
  • water-soluble organic compound As specific examples of the water-soluble organic compound according to the present embodiment, ethyl diglycol acetate, n-butanol, ethyl acetate, propylene glycol monomethyl ether acetate, ethylcellosolve, ethylene glycol monophenyl ether, pentanediol, isopropanol, 1,3-pentanediol, allyl alcohol, acetonitrile, 1-propanol, tetrahydro-2,4-dimethylthiophene 1,1-dioxide, diethylene glycol, dimethylformamide, ethylacetamide, ethylenediamine, diethyl sulfone, dimethylphosphite, phenylhydrazine, 2-methoxyethanol, butyrolactone, propylene glycol, ⁇ -caprolactam, ethanol, 3-methylsulfolane, N-nitrosodimethylamine, prop
  • water-soluble organic compound isopropanol, acetonitrile, diethylene glycol, ethylenediamine, 2-methoxyethanol, propylene glycol, ethanol, methanol, ethylene glycol, NN-dimethylformamide, glycerin, and the like are suitable.
  • the water-soluble organic compound remains in the coating after coating and baking. At this time, even if the boiling point or the sublimation point of the water-soluble organic compound is lower than the boiling point of water, the water-soluble organic compound remains in the coating after the coating and baking since the water-soluble organic compound and the metal phosphate interact with each other. In addition, in actual operation, a time taken to dry and bake the coating is about several seconds, and thus, also from this viewpoint, the water-soluble organic compound is to remain in the coating.
  • the boiling point of the water-soluble organic compound is preferably higher than the boiling point of water in the case where the water-soluble organic compound is liquid, and the sublimation point of the water-soluble organic compound is preferably higher than the boiling point of water in the case where the water-soluble organic compound is solid. More favorably, the boiling point or the sublimation point of the water-soluble organic compound according to the present embodiment is preferably 150°C or more, more preferably 200°C or more.
  • the boiling point or the sublimation point of the water-soluble organic compound according to the present embodiment is preferably less than 300°C. If the boiling point or the sublimation point of the water-soluble organic compound is 300°C or more, the water-soluble organic compound can cause surface tackiness and deliquescence.
  • the thickness of the insulating coating film is preferably about 0.3 to 5.0 ⁇ m, more preferably about 0.5 ⁇ m to 2.0 ⁇ m. By specifying the coating thickness of the insulating coating film within the range, it is possible to keep more excellent uniformity.
  • a production method for the non-oriented electrical steel sheet according to the present embodiment is a production method for producing a non-oriented electrical steel sheet that includes a base metal steel sheet and an insulating coating film.
  • the production method according to the present embodiment includes a step of applying the surface treatment agent described above to the surface of the base metal steel sheet and a step of heating the base metal steel sheet with the surface treatment agent applied thereto to form the insulating coating film. The steps will be each described below.
  • a surface treatment agent that includes 3 to 50 parts by weight of an organic resin and 5 to 50 parts by weight of a water-soluble organic compound per 100 parts by weight of a metal phosphate including at least aluminum and in which a solvent is water is applied to a surface of the base metal steel sheet.
  • a blending proportion of the metal phosphate, the organic resin, and the water-soluble organic compound in the surface treatment agent is to be a blending proportion of the metal phosphate, the organic resin, and the water-soluble organic compound in the insulating coating film after the application and drying.
  • the metal phosphate, the organic resin, and the water-soluble organic compound in the surface treatment agent the metal phosphate, the organic resin, and the water-soluble organic compound that are mentioned above to be used.
  • the content of the organic resin contained in the surface treatment agent is set to be 3 to 50 parts by weight per 100 parts by weight of the metal phosphate.
  • the content of the organic resin is set to be 3 to 50 parts by weight per 100 parts by weight of the metal phosphate.
  • the content of the organic resin is set to be 3 parts by weight or more, it is possible to control the degree of crystallinity of the aluminum phosphate to be 5.0% or less.
  • the degree of crystallinity of the aluminum phosphate to be 0.5% or more.
  • by setting the content of the organic resin to be 50 parts by weight or less it is possible to increase the concentration of the metal phosphate in a relative manner and ensure a heat resistance.
  • the content of the organic resin is, per 100 parts by weight of the metal phosphate, preferably 5 parts by weight or more, more preferably 6 parts by weight or more. In addition, the content of the organic resin is, per 100 parts by weight of the metal phosphate, preferably 40 parts by weight or less, more preferably 25 parts by weight or less.
  • the content of the water-soluble organic compound contained in the surface treatment agent is set to be 5 to 50 parts by weight per 100 parts by weight of the metal phosphate.
  • the degree of crystallinity of the aluminum phosphate is 5.0% or less.
  • the degree of crystallinity of the aluminum phosphate is 0.5% or more.
  • the content of the water-soluble organic compound is, per 100 parts by weight of the metal phosphate, preferably 6 parts by weight or more, more preferably 7 parts by weight or more.
  • the content of the water-soluble organic compound is, per 100 parts by weight of the metal phosphate, preferably 40 parts by weight or less, more preferably 25 parts by weight or less.
  • the surface treatment agent may further contain a nonionic surfactant.
  • the content of the nonionic surfactant is preferably 0.1 to 10 parts by weight per 100 parts by weight of the metal phosphate.
  • the content of the nonionic surfactant is, per 100 parts by weight of the metal phosphate, more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more.
  • the content of the nonionic surfactant is 10 parts by weight or less, it is also possible to prevent deterioration in corrosion resistance.
  • the content of the nonionic surfactant is, per 100 parts by weight of the metal phosphate, more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less.
  • an inorganic compound such as carbonate, hydroxide, oxide, titanate, and tungstate or antifoaming agent, viscosity regulator, antiseptic, leveling agent, brightener, or the like may be contained.
  • polymerization initiators including persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, organic peroxides such as t-butylhydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, and hydrogen peroxide, and the like can be used.
  • persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate
  • organic peroxides such as t-butylhydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide
  • hydrogen peroxide and the like
  • polymerization initiators include persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, organic peroxides such as t-butylhydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, and hydrogen peroxide, and the like
  • the surface treatment agent including the components described above is applied to the surface of the base metal steel sheet by various known application systems.
  • an application system there is no particular limitation on the application system to be used; a roll coater system may be used, or an application system such as a spraying system and a dipping system may be used.
  • the base metal steel sheet to which the surface treatment agent has been applied is heated to a predetermined heating temperature to form the insulating coating film.
  • the degree of crystallinity of the aluminum phosphate significantly depends on heating conditions. It is thus necessary to optimize the heating conditions based on a composition of the surface treatment agent.
  • the degree of crystallinity of the aluminum phosphate can be decreased by passing through a predetermined temperature range in which crystals of the metal phosphate start to precipitate in a short time when the surface treatment agent applied to the surface of the base metal steel sheet is dried and solidified.
  • the heating is performed particularly such that a heating rate for a range of 100 to 200°C falls within a range of 10 to 100°C/sec.
  • the degree of crystallinity tends to decrease with a decrease in the heating temperature, and the degree of crystallinity tends to increase with an increase in the heating temperature.
  • the heating temperature is to be set at 200°C to 360°C.
  • the heating temperature by setting the heating temperature at 200°C or more, the polymerization reaction of the metal phosphate proceeds efficiently, making it easy to provide water resistance and the like.
  • the heating temperature by setting the heating temperature at 360°C or less, it is possible to restrain the organic resin from being oxidized and to improve productivity.
  • the temperature at the start of the heating and the temperature may be a temperature near a room temperature.
  • the retention time at the heating temperature is thus set at 20 seconds or less. Note that, in a case where the metal phosphate does not contain the divalent metallic element M other than Al, the retention time at the heating temperature is set at less than 10 seconds because it is difficult to restrain the crystallization.
  • a cooling rate is set to be within a range of 10 to 50°C/sec from the heating temperature to 100°C.
  • the cooling rate is set to be 10°C/sec or more, it becomes possible to control the degree of crystallinity of the aluminum phosphate to be 5.0% or less.
  • the cooling rate is set at 20°C/sec or more because it is difficult to restrain the crystallization.
  • the cooling rate is set to be 50°C/sec or less, it becomes possible to control the degree of crystallinity of the aluminum phosphate to be 0.5% or more.
  • a heating system for performing the heating a typical radiant heater or air-heating furnace is available, and heating using electricity such as an induction heating system may be used.
  • base metal steel sheets that included chemical components consisting of, in mass%, Si: 3.1%, Al: 0.6%, and Mn: 0.2%, with the balance being Fe and impurities, had a sheet thickness of 0.30 mm, and had an arithmetic average roughness Ra of 0.32 ⁇ m were used.
  • treatment liquids having compositions shown in Table 1 were applied such that an amount of application is 1.0 g/m 2 , and the base metal steel sheets were subjected to baking under the conditions shown in Table 2.
  • types and SP values of water-soluble organic compounds and organic resins shown in Table 1 are shown in Table 3 and Table 4.
  • the heating rates each mean an average heating rate for from the 100°C to 200°C
  • the retention times each mean a time of retention at the corresponding heating temperatures
  • the cooling rates each mean an average cooling rate for from the heating temperatures to 100°C.
  • Heating rate (°C/s) Heating temperature (°C) Retention time (s) Cooling rate (°C/s) 1 80 320 8 30 2 60 320 10 30 3 60 320 15 20 4 80 280 8 20 5 80 280 8 20 6 80 220 10 10 7 80 220 10 20 8 40 350 8 30 9 40 250 8 30 10 12 250 10 20 11 40 350 8 30 12 80 350 15 20 13 60 220 5 20 14 80 220 5 30 15 80 220 10 30 16 80 220 10 20 17 80 320 5 30 18 80 220 8 20 19 40 320 8 30 20 40 280 8 20 21 60 280 10 20 22 60 280 10 20 23 60 280 10 20 24 60 280 10 20 25 15 380 6 20 26 6 250 10 20 27 150 320 5 30 28 60 320 5 30 29 10 350 20 40 30 20 320 30 30 31 10 320 6 15 32 20 320 10 8
  • metal phosphate treatment liquids are prepared by mixing and stirring orthophosphoric acid, and hydroxides, oxides, and carbonates of metals such as Al(OH) 3 , ZnO, and Mg(OH) 2 , and the metal phosphate treatment liquids are made into their 40 mass% aqueous solutions. Note that the reagents used were all commercially available. Table 1 shows the blending amounts of aluminum phosphate in metal phosphates, and the blending amounts of other metal phosphates in the metal phosphates in terms of parts by weight.
  • the water-soluble organic compounds and the organic resins used are also commercially available and have SP values shown in Table 3 and Table 4.
  • the blending proportions of the metal phosphate, the water-soluble organic compound, and the organic resin in each of the treatment liquids shown in Table 1 are the blending proportions of the metal phosphate, the water-soluble organic compound, and the organic resin in each of the insulating coating films after the application and the drying.
  • Samples of the obtained non-oriented electrical steel sheets were subjected to the measurement by X-ray diffractometry, by which degrees of crystallinity of the aluminum phosphate were determined. Conditions for measuring the XRD spectrum were as mentioned above.
  • steel sheet samples with adhesive tapes attached thereto were wound around metal bars having diameters of 10 mm, 20 mm, and 30 mm, then the adhesive tapes were torn off, and the adhesiveness was evaluated from traces of the tearing.
  • a sample that was not torn off even when the sample was bent around 10 mm ⁇ was given a grade "A”
  • a sample that was not torn off when the sample was bent around 20 mm ⁇ was given a grade "B”
  • a sample that was not torn off when the sample was bent around 30 mm ⁇ was given a grade "C”
  • a sample that was torn off was given a grade "D”.
  • samples that were given the grade "A” or "B” were rated as good.
  • a sample of a surface insulation resistance of less than 5 ⁇ cm 2 /sheet was given a grade "D”
  • a sample of a surface insulation resistance 5 ⁇ cm 2 /sheet or more to less than 10 ⁇ cm 2 /sheet was given a grade "C”
  • a sample of a surface insulation resistance of 10 ⁇ cm 2 /sheet or more to less than 50 ⁇ cm 2 /sheet was given a grade "B”
  • a sample of a surface insulation resistance of 50 ⁇ cm 2 /sheet or more was given a grade "A”.
  • samples that were given the grade "A” or "B” were rated as good.
  • Heat resistance was evaluated in terms of corrosion resistance after stress relieving annealing.
  • the samples were subjected to heat treatment for 1 hour in a 100%-nitrogen atmosphere at 850°C and subsequently left in a temperature and humidity controlled chamber at a temperature of 50°C and a humidity of 90% for 48 hours, and an area fraction of rust occurred on the surface of each sample was evaluated as in the evaluation of corrosion resistance. Evaluation criteria are shown below; grades 9 and 10 were determined as "A”, grades 6, 7, and 8 were determined as “B”, grades 4 and 5 were determined as "C”, grades 1, 2, and 3 were determined as "D”, and samples given the grades "A” or "B” were rated as good.
  • the breaking load of each sample was measured and used as an index for workability.
  • a cutting blade was set to come into contact perpendicularly with the sample worked into 3 cm ⁇ 6 cm, and a load under which the sample was broken was measured.
  • the breaking load was compared with a breaking load of a sample with no insulating coating film applied thereto; a ratio between the breaking loads being less than 0.95 was determined as "A”, the ratio being 0.95 or more to less than 1.00 was determined as "B", the ratio being 1.00 or more to less than 1.05 was determined as "C”, the ratio being 1.05 or more to less than 1.10 was determined as "D”, and the ratio being 1.10 or more was determined as "E”. Samples given the grades "A” or "B” for the workability were rated as good.
  • Corrosion resistance was evaluated in conformity to the salt spray test according to the JIS (JIS Z2371:2015). Specifically, each sample underwent 5 cycles each including a step of spraying 5%-NaCl aqueous solution in an atmosphere at 35°C for 1 hour on the sample, a step of retaining the sample in an atmosphere at a temperature of 60°C and a humidity of 40% for 3 hours, and a step of retaining the sample in an atmosphere at a temperature of 40°C and a humidity of 95% for 3 hours, and then an area fraction of rust occurring on the surface of the sample was evaluated on a 10-point scale. Evaluation criteria are shown below. Samples given a grade of 5 or more for corrosion resistance were rated as good.
  • Hygroscopic resistance was evaluated by exposing the samples in a temperature and humidity controlled chamber in which a temperature is adjusted to 50°C, and a humidity is adjusted to 90%, for 720 hours, and then area fractions of rust occurring on their surfaces were determined by visual check. Evaluation criteria are shown below. Samples given a grade of 3 or more for hygroscopic resistance were rated as good.
  • the thickness of its insulating coating film was measured with an electrical coating thickness tester, and a space factor (%) was calculated from measurement values of the insulating coating film on the surfaces of its base metal steel sheet and the sheet thickness of the base metal steel sheet (300 ⁇ m).
  • samples in example embodiments of the present invention satisfying the specifications according to the present invention did not contain chromate and exhibited much more excellent properties in insulation property, workability, adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance.
  • samples in comparative examples falling out of any one of the specifications according to the present invention did not provide properties combining insulation property, workability, adhesiveness, hygroscopic resistance, corrosion resistance, and heat resistance.

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